US7175762B1 - Nanocarpets for trapping particulates, bacteria and spores - Google Patents
Nanocarpets for trapping particulates, bacteria and spores Download PDFInfo
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- US7175762B1 US7175762B1 US10/455,873 US45587303A US7175762B1 US 7175762 B1 US7175762 B1 US 7175762B1 US 45587303 A US45587303 A US 45587303A US 7175762 B1 US7175762 B1 US 7175762B1
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Definitions
- the present invention is directed to the growth of dense mats or carpets of nanotubes, and more particularly to the growth of dense carpets of carbon nanotubes for use in trapping small particles for in-situ detection.
- Nanoscale structures are becoming increasingly important because they provide the basis for devices with dramatically reduced power and mass, while simultaneously having enhanced capabilities, and previous patent applications have disclosed the advantageous use of such nanostructures in a number of different real-time, molecule specific sensors.
- Activated carbon is a carbonaceous adsorbent with high internal porosity, and hence a large internal surface area of 500 up to 1500 m ⁇ 2/g.
- Activated carbon mainly consists of elementary carbon in a graphite-like structure. It can be produced by heat treatment, or “activation”, of raw materials such as wood, coal, peat and coconuts. During the activation process, the unique internal pore structure is created, and it is this pore structure which provides activated carbon its outstanding adsorptive properties.
- Activated carbon finds uses in a myriad of applications, from adsorption or chemisorption, to removal of chlorine through reduction reactions, as a carrier of catalytic agents, as a support material for biofilters, or as a chemical carrier for the slow release of coloring agents.
- high surface area activated charcoal is an excellent trapping material
- the three-dimensional nature of the high surface area matrix makes it very difficult to use standard detection schemes, laser diagnostics techniques (UV fluorescence and other non-linear light scattering techniques) to actually distinguish the particles of interest (such as those containing proteins, nucleic acids, and coenzymes) from other organic and inorganic particulate contaminants.
- the present invention is directed to a nanofeature particulate trap comprising a plurality of densely packed nanofeatures, such as nanotubes.
- the invention is also directed to a particulate detector incorporating the nanofeature particulate trap.
- the nanofeature particulate trap is substantially two-dimensional.
- the nanofeatures are hydrophobic.
- the nanofeature trap may be particularly suited for liquid environments.
- the nanofeatures are chosen to have a large surface-to volume ratio such that surface interactions are promoted.
- the radius of curvature of the nanofeatures is confined to provide a nanofeature trap having large Van der Waals forces.
- the nanofeature trap is in communication with a voltage source such that an electrical field can be generated in the individual nanofeatures of the nanofeature trap.
- the individual nanofeatures may be designed to serve as electron emitting/receiving elements.
- the application of an electrical field to the nanofeatures is designed to trigger an electromechanical actuation of the individual nanofeatures.
- the nanotrap actuator comprises a nanotrap with an integrated electrode substrate. The nanoscale actuators of the present invention are designed to provide the capability of controllable motion on near-atomic scales. In such an embodiment, the transduction mechanism is symmetric—length changes in the nanotubes will induce charge transfer and hence voltages.
- the nanofeature trap is designed to trap particles as small as 0.5 micron.
- This invention is also directed to an analyzer, which utilizes a nanofeature trap in combination with a detector that functions as a molecular sensor.
- This invention is also directed to novel systems and methods for utilizing nanofeature traps comprising a plurality of densely packed nanotubes with integrated detectors to form a particulate analyzer.
- the invention is directed to a system for the detection of substances comprising multiple nanofeature traps as described above, such that parallel processing of molecules can be carried out.
- This invention is also directed to growth and processing techniques to control the physical properties of the individual nanotubes and the density of the trap generally; and methods for positioning the nanotube trap during growth, including nanoscale patterning of the substrate to ensure that the growth of the nanotube trap is located and aligned with any external analysis devices.
- the nanotubes comprising the nanofeature trap are self-assembled to have a specified diameter, a specified height, and a specified degree of curling suitable for use in the devices of the current invention.
- the substrate for the trap is made of a semiconductor such as, for example, oxidized silicon or aluminum oxide, coated with a metal catalyst film such as, for example, Ni or Co.
- the silicon can be further doped to adjust the electronic properties of the substrate surface.
- the nanotubes comprising the nanofeature trap are self-assembled from an inert material such as, for example, carbon utilizing a carbon feedstock gas such as, for example, ethylene.
- FIG. 1 is a schematic view of an embodiment of a nanotube trap in operation according to the invention.
- FIG. 2 is a side view micrograph picture of an embodiment of a nanotube trap according to the invention.
- FIG. 3 is a top view micrograph picture of an embodiment of a nanotube trap according to the invention.
- FIG. 4 is a top view micrograph picture of an embodiment of a nanotube trap entrapping Bacillus pumilus according to the invention.
- FIG. 5 is a close-up of a top view micrograph picture of an embodiment of a nanotube trap entrapping Bacillus pumilus according to the invention.
- FIG. 6 is a flowchart of an exemplary detection scheme according to the invention.
- FIG. 7 is a schematic view of an embodiment of an actuated nanotube trap according to the invention.
- FIG. 8 is a graphical depiction of the electromechanical response of a prior art mat of nanofeatures.
- FIG. 9 is a schematic of an apparatus for growing the nanotube trap according to the invention.
- the present invention is directed to a nanofeature particulate trap comprising a plurality of densely packed nanofeatures, such as nanotubes.
- the invention is also directed to a particulate detector incorporating the nanofeature particulate trap. These devices will be collectively referred to as nanotraps herein.
- the nanotrap device 10 generally comprises a substrate 12 , having a growth surface 14 that can additionally be coated with a catalyst to encourage nanofeature growth.
- a layer 16 of densely packed nanofeatures capable of entrapping particulates of less than 10 microns is then grown on top of the growth surface of the substrate.
- the nanofeatures comprise a plurality of nanotubes 18 arranged such that the nanotubes originate and grow normal to the growth surface. Side and top view micrographs of exemplary nanotube nanotraps are shown in FIGS. 2 and 3 .
- nanotube nanofeature is shown in FIGS. 1 to 3 , it should be understood that any suitable nanofeature capable of tuned oscillation may be utilized.
- a plurality of carbon nanotubes are utilized.
- Carbon nanotubes possess a combination of properties that make them well suited for use as nanofeatures in a nanotrap.
- nanotubes combine a nanometer scale diameter with a large aspect ratio, good electrical conductivity, and elastic bending.
- the small radius of curvature of the nanotubes induces large Van der Walls forces contributing to the “sticking” capabilities of the individual nanotubes.
- Carbon nanotubes are also hydrophobic facilitating the interaction of bio particulates with the nanotrap in liquid environments.
- Single-wall nanotubes also have a Young's modulus of approximately 1 TPa, which corresponds to strength/weight ratio approaching 200 times that of steel.
- the combination of this high Young's modulus and the ability to withstand large strains ( ⁇ 5%) suggests that SWNTs should also have very high breaking strengths.
- the nanotraps shown in FIGS. 1 to 3 utilize the inherently large surface-to-volume ratio of the mats of nanofeatures to promote surface interactions with particulates in the surrounding environment. This is analogous to the operation of the cilia in the lungs, trachea, and nasal epithelia of the human body, which functions similarly as a trap to filter out particulates in the body. Once the particulates come into contact with the nanofeatures of the nanotrap, the above recited properties of the nanofeatures serve to trap the particulates on the nanotrap.
- the application of relatively small voltages can propogate large electric fields in nanotubes.
- the electric field thus generated can be used to draw and trap particulates onto the nanotrap through electrostatic interactions.
- nanotubes can be controlled to control the length, diameter and tip curvature or curliness to allow for the possibility of engineering a nanotrap to have particular trapping preference for specifically sized particulates.
- FIGS. 4 and 5 show the results of an experiment using an exemplary embodiment of the nanotrap according to the current invention having nanotube nanofeatures approximately 10 microns long.
- the nanotrap was submerged in a solution containing biological spores of Bacillus pumilis . As shown, the nanotraps interact with and trap the Bacillus pumilis spores onto the surface of the nanotrap.
- the nanotrap is designed to be incorporated into a detection scheme such that the trapped particulates can be analyzed.
- the detector can be operated in two distinct modes.
- the nanotrap having the particulates embedded thereon can be interrogated in-situ by the detector to analyze the trapped particulates.
- all the particulates within a nanotrap could be analyzed at once.
- the particles once trapped are released into the detector through some medium, such as a liquid solution for subsequent analysis.
- some medium such as a liquid solution for subsequent analysis.
- the nanotrap can be washed with either a liquid or gas stream to dislodge the particulates, and then this liquid or gas stream can itself be analyzed through any suitable technique.
- the particles can be dislodged by application of a force to the nanofeatures directly. For example, as discussed above, the application of an electrical field can increase the electrostatic forces between particulates and the nanotrap.
- the present invention is also directed to an actuated or active nanotrap device 20 , which would allow for the active dislodgement of trapped particulates.
- an actuated nanotrap is shown schematically in FIG. 7 .
- the nanotubes 22 act as a transducer, converting an input signal 24 into a mechanical action 26 , shown in the figures as the dashed nanotubes.
- a voltage is applied to the nanotubes to create a charge on the tube and thereby produce a deflection of the individual nanotubes, corresponding to an expansion (which in one embodiment is an elongation) when the tubes are negatively-biased and a contraction when the tubes are positively-biased.
- This charge induced motion has previously been observed in random arrays of carbon bimorph mats and in graphite sheets, see, e.g., Baughman et al., Science, 284 1340 (1999), incorporated herein by reference.
- the nanotube length change is caused by “quantum chemical effects”, that is, changes in orbital occupation and band structure result in changes in the C—C bond distances and thus the length of the nanotube.
- quantum chemical effects that is, changes in orbital occupation and band structure result in changes in the C—C bond distances and thus the length of the nanotube.
- the Baughman experiments were done in electrolytic solutions, it should be understood that no electrolytic solution is required so long as direct electrical contact is made with each nanotube.
- the charge-induced actuation mechanisms shown in FIG. 7 is only depicted in non-liquid environments, it should be understood that the nanotube electromechanical transduction effect can be compatible with operation in liquids, such as for use in trapping particulates in solution.
- the actuated nanotrap device shown schematically in FIG. 7 functions basically as an oscillator.
- each individual nanotube 22 acts as a transducer, converting an input bias 24 into a mechanical oscillation 26 .
- a bias from a tuning control source 28 can be capacitively coupled to the nanotrap such that this bias can be used to control the stress on the rigidly anchored nanotubes 22 , thereby allowing for the tuning of the nanotube's mechanical response.
- An additional RF bias can also be applied to vary the length of the nanotubes at an RF frequency, thereby producing an oscillating deflection of the nanotrap structure.
- the substrate can be made of any material which can withstand the temperatures required for growth of the nanofeatures and which can be optionally modified to provide a nucleation area for controllably positioning the nanotrap on a specified area of the substrate for integration with a suitable nanomechanical device.
- suitable substrates include metallized Si oxide wafers, alumina, or sapphire.
- any suitable catalyzing metal can be used for the nucleation area on the surface of the substrate, such as, for example, nickel or cobalt.
- the catalyzing metal could be an alloy of two or more metals such as a Co/Ni or Ti/Ni alloy.
- the metal catalysts could also be produced by pyrolysis of inorganic or organic metal-containing compounds, such as, for example, Ferric Nitrate or Cobalt Chloride. Although not necessary for the current invention such catalyst regions could be controlled to a limit of sub-50 nm catalyst dots, thus it is possible to nucleate growth of a single nanotube at a catalyst location providing more than adequate control for ensuring proper placement of the nanotrap within a larger nanodetector.
- integrated electrodes can also be produced by combining the catalyst regions with non-catalytic or catalytic electrodes. This ability to precisely locate and orient the growth of the nanotrap and make electrical contact to the nanofeatures provides the basis for fabrication of an actuated nanotrap structure.
- Such a method may utilize an electron-beam lithography system.
- This invention is also directed to a method for growing the dense mats of nanofeatures on a substrate utilizing a chemical vapor deposition (CVD) technique.
- CVD chemical vapor deposition
- the nanotube growth is controlled by pre-patterning growth regions into Si or Si-on-Insulator (SOI) wafers.
- the basic technique to construct the alignment structures uses a suitable substrate, such as Si or SOI.
- a suitable substrate such as Si or SOI.
- the region upon which the nanofeatures are to grow may be coated with a thin catalyst film such as Ni, Co, or other metal-based mixtures or compounds to nucleate nanofeature growth.
- a chemical vapor deposition process is utilized to grow the nanotubes from the catalyst patterns.
- a high pressure CVD process uses methane, ethylene, or carbon monoxide in pure form or in a mixture with hydrogen (or ammonia) and argon (or nitrogen) to produce nanotubes on a substrate heated to approximately 500–1000 C.
- the nanofeatures comprising the nanotrap can be of any shape and made by any process and from any material suitable for making self-assembled structures capable of acting in conjunction to trap particulates having dimensions at least as small as 10 micron, such as, for example, spheres or pyramids made of other atomic materials or even biomolecules, such as, for example, proteins.
- the nanofeatures may be further functionalized for a variety of applications, such as, for example, being made hydrophilic or hydrophobic, being charged either negatively or positively, or being derivatized with specific chemical groups, etc.
- in situ sidewall treatments could alter the electrical properties of the nanotubes, such as by increasing the charge differential induced by a given applied voltage.
- a nanomechanical device such as a detector according to the invention may also include a body, a self-contained power supply, and any additional machinery or circuitry necessary for the device's operation.
- the body of the nanomechanical device itself can be made of any material suitable for micromachining utilizing standard lithographic or MEMS techniques to enclose the nanotrap, such as, for example, aluminum oxide or silicon.
- the body further comprises a cap layer, which can be of any design, such that the cap layer protects the nanotrap from unwanted contact with the external environment.
- a cap layer could be made of any suitable material, such as, for example, aluminum oxide or silicon.
- Such a cap layer could be formed by any conventional MEMS process, such as growth or deposition over a sacrificial layer (not shown) deposited to encapsulate the self-assembled nanotrap wherein the sacrificial layer can subsequently be removed to expose the self-assembled nanotrap itself.
- these support structures could be formed in a single deposition step with the self-assembled nanotrap.
- one of the substrate, the cap layer, or walls of the nanomechanical device is transparent such that an optical source can be used to interrogate or activate the nanotrap.
- the nanomechanical device may comprise an array of multiple nanotraps such that multiple or parallel processing can be carried out at one time.
- the nanotraps can be integrated into a single circuit or detector, such as a laser based particle analyzer. It should be understood that while arrays of nanotraps are discussed above, any suitable alternative geometry of nanotraps may be utilized. Such an embodiment could be used to develop a mobile nanotrap detector device on a chip for mobile detection and analysis of samples. In such an embodiment a portable power source (not shown) would also be integrated into the device.
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Abstract
Description
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WO2005001021A3 (en) | 2005-05-12 |
AU2003304252A1 (en) | 2005-01-13 |
US20070039858A1 (en) | 2007-02-22 |
WO2005001021A2 (en) | 2005-01-06 |
AU2003304252A8 (en) | 2005-01-13 |
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